JP2014511351A - Gas phase catalytic fluorination - Google Patents

Abstract

The present invention is a fluorination method comprising alternately a reaction stage and a regeneration stage, the reaction stage comprising producing a fluorinated product by reacting a chlorinated product with hydrogen fluoride in a gas phase in the presence of a fluorination catalyst. And a method wherein the regeneration step comprises contacting the fluorination catalyst with an oxidant-containing gas stream.

Description

  The present invention relates to a method for producing a fluorinated product by gas phase catalytic fluorination of chlorinated product using hydrogen fluoride (HF), particularly 2-chloro-3,3,3-trifluoro-1-propene (HFCO- 1233xf) or 1,1,1,2,3-pentachloropropane to produce 2,2,2,3-tetrafluoropropene (HFO-1234yf) by vapor phase catalytic fluorination.

  The product obtained by the present invention, such as HFO-1234yf, is a known compound for foaming agents, refrigerants, aerosol propellants, heat transfer media, fire extinguishers, and other applications. This HFO-1234yf is a compound having a zero ozone depletion potential (ODP), and is also known to have a very low global warming potential (GWP) of 150 or less.

The use of chlorofluorocarbons (CFCs) was prohibited by the Montreal protocol for ozone layer protection. Instead of chlorofluorocarbons, compounds with less impact on the ozone layer, such as hydrofluorocarbons, HFCs such as HFC-134a, have come to be used. However, these compounds were proved to be greenhouse gases responsible for global warming and were regulated by the Kyoto Protocol on Climate Change. As concerns over global climate change continue, there is an increasing need to develop methods to replace those with high ODP (ozone depletion potential) and high GWP (global warming potential). Hydrofluorocarbons (HFCs) are compounds that do not affect the ozone layer and have been identified as alternatives to chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) as solvents, cleaning agents, and heat transfer fluids, Nevertheless, it tends to show a significantly higher GWP value. Hydrofluoroolefins (HFO) are considered to be a potential alternative with zero ODP values and low GWP values.
Therefore, a method for producing this HFO compound, particularly HFO-1234yf, has been developed.

Patent Document 1 (International Patent Publication No. WO 2007/079431) discloses a method for producing a fluorinated olefin such as hydrofluoropropene. A process described extensively as a single reaction or more than one reaction is a fluorination of a compound of formula C (X) _m CCl (Y) _n C (X) _m with at least one formula CF ₃ CF═CHZ. Producing the compound. Here, each X, Y and Z is independently H, F, Cl, I or Br, each m is independently 1, 2 or 3, and n is 0 or 1. HFO-1234yf is prepared by fluorinating HFCO-1233xf to 1,1,1,2-tetrafluoro-2-chloropropane (HCFC-244bb) followed by dehydrochlorination.
HFCO-1233xf is prepared by fluorination of the corresponding chlorinated precursor (CCl ₂ = CClCH ₂ Cl).

  Patent document 2 (European Patent Publication No. EP-A-939071) includes, among many possibilities, fluorinated propenes (eg, HFO-) by vapor phase fluorination of halogenated propenes in a very long list. 1234yf list) is disclosed.

  Patent Document 3 (International Patent Publication No. WO 2008/054781) discloses various fluoropropanes and various halofluoropropenes by reacting halopropane or halopropene with HF, optionally in the presence of a catalyst. A manufacturing method is disclosed. Patent Document 3 discloses an HFO produced by reacting 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) in the presence of HF over a catalyst, particularly Cr / Co (98/2). A method for producing -1234yf is disclosed. The reaction products include HFO-1234yf and HFCO-1233xf, the latter being the main product, the other products being 1-chloro-3,3,3-trifluoro-1-propene (HFCO-1233zd) and 1 1,1,2,2-pentafluoropropane (HFC-245cb) and 1,3,3,3-tetrafluoro-1-propene (HFO-1234ze).

  Patent Document 4 (International Patent Publication No. WO 2008/002500) discloses HFO-by catalytic conversion of 1,1,1,2,3-pentafluoropropane (HFC-245eb) over a dehydrofluorination catalyst. A process for producing a mixture of 1234yf and HFO-1234ze is disclosed.

  In Patent Document 5 (International Patent Publication No. WO2008 / 040969), HCFC-243db is dehydrochlorinated to produce HFCO-1233 (xf and zd), followed by 1,1,1,2-tetrafluoro A process is disclosed that includes a reaction involving the production of -2-chloropropane (HCFC-244bb) and subsequent production of the desired HFO-1234yf by dehydrochlorination. In Example 1 of this document, HFO-1234yf and HFCO-1233xf are produced by gas phase reaction of HCFC-243db with HF at atmospheric pressure over a Zn / chromia catalyst, and a small amount of HFC-245cb is also produced. It is disclosed.

  Patent Document 6 (International Patent Publication No. WO2009 / 015317) includes 1,1,2,3-tetrachloro-1-propene (HCO-1230xa), 1,1,1,2,3-pentachloropropane (HCC). -240db) or a chlorinated product such as 2,3,3,3-tetrachloro-1-propene (HCO-1230xf) on a catalyst in the gas phase in the presence of at least one stabilizer. Is disclosed. In this way, 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf) is obtained.

Patent Document 7 (US Patent Publication No. US2009 / 0240090) includes formula (I) CX ₂ = CClCH ₂ X or formula (II) CX ₃ CCl = CH ₂ or formula (III) CX ₃ CHClCH ₂ X ( Here, a process for the production of 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf) starting from a compound of X = F, Cl, Br, I) is disclosed. This method involves three stages, after which purification can be carried out. This process includes a recycle stage that allows for higher conversions and yields.

  Patent Document 8 (International Patent Publication No. WO 2010/123154) starts from HFCO-1233xf by reacting HFCO-1233xf with HF in the presence of oxygen and a catalyst containing chromium oxide or fluorinated chromium oxide. There is a method of manufacturing HFO-1234yf.

International Patent Publication No. WO 2007/079431 European Patent Publication No. EP-A-939071 International Patent Publication No. WO 2008/054781 International Patent Publication No. WO 2008/002500 International Patent Publication No. WO2008 / 040969 International Patent Publication No. WO2009 / 015317 US Patent Publication No. US2009 / 0240090 International Patent Publication No. WO 2010/123154

  However, there is a need to provide an improved process for producing fluoroolefins, such as HFO-1234yf, which have particularly improved conversion and / or improved selectivity and / or are effective over a longer period of time. There is still.

  The present invention relates to a fluorination method comprising alternately a reaction stage and a regeneration stage, wherein the reaction stage is a gas phase reaction of chlorinated product with hydrogen fluoride in the presence of a fluorination catalyst. And a regeneration step comprising contacting the fluorination catalyst with an oxidant-containing gas stream.

  In one embodiment of the present invention, the fluorination process includes a preactivation stage that includes contacting a fluorination catalyst with an oxidant-containing gas stream.

  In one embodiment of the invention, the oxidant-containing gas stream of the activation and / or regeneration stage is an oxygen-containing gas stream.

  In one embodiment of the present invention, the activation stage and / or regeneration stage comprises fluorinating catalyst with an oxidant-containing gas stream for at least 2 hours, preferably at least 4 hours, more preferably at least 10 hours, even more preferably at least 15 Including contacting for hours.

  In one embodiment of the present invention, the oxidant-containing gas stream of the activation stage and / or regeneration stage includes hydrogen fluoride in addition to the oxidizer, and the oxidant-containing gas stream of activation stage and / or regeneration stage. The ratio of the oxidizing agent is preferably 2 to 98 mol%, more preferably 5 to 50 mol%, based on the total amount of the oxidizing agent and hydrogen fluoride.

  In one embodiment of the invention, the oxidant-containing gas stream of the activation stage and / or regeneration stage is free of hydrogen fluoride and is preferably air.

In one embodiment of the present invention, the activation and / or regeneration step comprises contacting the fluorination catalyst with a hydrogen fluoride gas stream in (1) or (2) below:
(1) before contacting the fluorination catalyst with the oxidant-containing gas stream, or (2) after contacting the fluorination catalyst with the oxidant-containing gas stream.

  In one embodiment of the present invention, the activation stage includes a preliminary stage in which the chloride is vapor phase reacted with hydrogen fluoride in the presence of a fluorination catalyst prior to contacting the chloride with the oxidant-containing gas stream.

  In one embodiment of the invention, the oxidant-containing gas stream is contacted with the fluorination catalyst at a temperature of 250-500 ° C., preferably 300-400 ° C., more preferably 350-380 ° C. in the activation stage and / or regeneration stage. Let

  In one embodiment of the invention, the fluorinated product is a fluoroolefin, preferably fluoropropene, more preferably 2,3,3,3-tetrafluoro-1-propene.

  In one embodiment of the invention, the chlorinated product is selected from hydrochlorocarbons, hydrochlorofluorocarbons and hydrochlorofluoroolefins, preferably 2-chloro-3,3,3-trifluoro-1-propene, 1,1 , 1,2,3-pentachloropropane, 1,1,2,2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, 2,3,3,3-tetrachloro- It is selected from 1-propene and 1,1,2,3-tetrachloro-1-propene, more preferably 2-chloro-3,3,3-trifluoro-1-propene.

  In one embodiment of the invention, the fluorination catalyst is a supported catalyst, preferably supported on a support selected from fluorinated alumina, fluorinated chromia, fluorinated activated carbon or graphite carbon.

In one embodiment of the invention, the fluorination catalyst is an unsupported catalyst.
In one embodiment of the invention, the fluorination catalyst is selected from Co, Zn, Mn, Mg, V, Mo, Te, Nb, Sb, Ta, P, Ni or mixtures thereof, preferably Ni. It further comprises a cocatalyst and is preferably present in an amount of about 1-10% by weight of the fluorination catalyst.

  In one embodiment of the invention, the fluorination catalyst is a hybrid chromium / nickel catalyst with an atomic ratio of nickel to chromium of preferably 0.5-2, more preferably about 1.

In one embodiment of the invention, the molar ratio of hydrogen fluoride: 2-chloro-3,3,3-trifluoro-1-propene is 3: 1 to 150: 1, preferably 4: 1 to 70: 1. More preferably 5: 1 to 50: 1, and still more preferably 10: 1 to 30: 1.
In one embodiment of the invention, the reaction stage is carried out at a pressure of 1-20 bar, preferably 5-15 bar, more preferably 7-10 bar.

In one embodiment of the invention, the reaction stage is carried out at a temperature of 200-450 ° C, preferably 300-430 ° C, more preferably 320-420 ° C, and even more preferably 340-380 ° C.
In one embodiment of the present invention, the contact time between hydrogen fluoride and chlorinated product in the reaction stage is 6 to 100 seconds, preferably 10 to 80 seconds, more preferably 15 to 50 seconds.

  In one embodiment of the present invention, the reaction step is carried out with an oxidation of 0.05 to 15 mol%, more preferably 0.5 to 10 mol%, more preferably 5 to 10 mol%, based on the total amount of chlorinated products and oxygen. It is carried out in the presence of an agent such as oxygen.

  The present invention satisfies the needs described in the background art above. In particular, the present invention provides an improved process for producing fluoroolefins such as HFO-1234yf. For example, the conversion of HFCO-1233xf is improved as compared to Patent Document 8 (International Patent No. WO 2010/123154). This result is made possible by the surprising discovery made by the inventor that the performance of the reaction increases over time when the fluorination catalyst is regenerated in the presence of an oxidant such as oxygen.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description. Unless otherwise indicated, the percentage is mol%.
Fluorination reaction In the fluorination reaction of the present invention, a chlorinated product is converted to a fluorinated product by reaction with hydrogen fluoride (HF) in the presence of a catalyst.
“Chloride” can be any molecule having a chlorine atom, and “fluoride” can be any molecule having a fluorine atom.
Chlorides are linear or branched (preferably having one or more substituents selected from F, Cl, I and Br (preferably F and Cl), wherein at least one of the substituents is Cl. It is preferably a straight-chain) C2 or C3 or C4 or C5 alkane or alkene compound.

  The fluorinated product has one or more substituents selected from F, Cl, I and Br (preferably F and Cl), and at least one of the substituents is linear or branched (preferably A linear) C2 or C3 or C4 or C5 alkane or alkene compound (preferably an alkene) is preferred.

  The chlorinated compound is a C3 alkane or alkene compound having one or more substituents selected from F, Cl, I and Br (preferably F and Cl), and at least one of the substituents being Cl. More preferably, the compound is a C3 alkene compound having one or more substituents selected from F, Cl, I and Br (preferably F and Cl), wherein at least one of the substituents is F.

  In a variant of the invention, the chlorinated product has a C4 alkane having one or more substituents selected from F, Cl, I and Br (preferably F and Cl), wherein at least one of the substituents is Cl. Or a alkene compound, wherein the fluoride has one or more substituents selected from F, Cl, I and Br (preferably F and Cl), and at least one of the substituents is F C4 alkene compound.

In one embodiment of the invention, the fluorinated product is a hydrofluoroolefin (and thus has no chlorine substituents).
During the reaction, it is preferred to substitute at least one Cl substituent in the chlorinated product with an F substituent.

  Conversion of chlorinated products to fluorinated products includes direct conversion (ie, conversion in a single reaction stage or essentially under one reaction condition) and indirect conversion (ie, by two or more reaction stages or two or more reactions). Conversion using conditions).

More preferred fluorination reactions are as follows:
(1) Reaction from 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);
(2) Reaction from 1,1,1,2,3-pentachloropropane (HCC-240db) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);
(3) Reaction from 1,1,2,2,3-pentachloropropane (HCC-240aa) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);
(4) Reaction from 2,3 dichloro-1,1,1-trifluoropropane (HCFC-243db) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);
(5) Reaction from 1,1,2,3 tetrachloro-1-propene (HCO-1230xa) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);
(6) Reaction from 2,3,3,3 tetrachloro-1-propene (HCO-1230xf) to 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf);
(7) Reaction from 1,1,1,2,3-pentachloropropane (HCC-240db) to 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);
(8) Reaction of 1,1,2,2,3-pentachloropropane (HCC-240aa) to 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);
(9) Reaction of 2,3 dichloro-1,1,1-trifluoropropane (HCFC-243db) to 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);
(10) Reaction of 1,1,2,3 tetrachloro-1-propene (HCO-1230xa) to 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf);
(11) Reaction from 2,3,3,3 tetrachloro-1-propene (HCO-1230xf) to 2-chloro-3,3,3-trifluoro-1-propene (HFCO-1233xf).

The fluorination reaction can be carried out at an HF molar ratio of generally 3: 1 to 150: 1, a contact time of 6 to 100 seconds and a pressure from atmospheric pressure to 20 bar. The catalyst bed temperature can be 200-450 ° C.
In order to prevent fast deactivation of the catalyst during the fluorination reaction, an oxidant (eg oxygen or chlorine) can be added, for example in a ratio of 0.05 to 15 mol% with respect to the mixture of oxidant and chlorate.

Catalyst The fluorination catalyst used in the present invention can be a supported or unsupported catalyst.
The catalyst is, for example, a metal based on a transition metal oxide or a derivative thereof or a halide or oxyhalide based on this metal. The catalyst is, for example, FeCl ₃ , chromium oxyfluoride, chromium oxide (which may be fluorinated if necessary), chromium fluoride and mixtures thereof.
Other possible catalysts are carbon supported catalysts, antimony based catalysts, aluminum based catalysts (eg AlF ₃ and Al ₂ O ₃ and alumina oxyfluorides and aluminum fluoride).

Commonly used catalysts are supported or non-containing, including chromium oxyfluoride, aluminum fluoride and oxyfluoride and metals such as Cr, Ni, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb, Mg. It is a supported catalyst. Moreover, the 7th page of patent document 9, the 1st line, the 5th line, the 28th line, the 32nd line, paragraph [0022] of patent document 10, the 9th page of patent document 11, the 22nd line, and the 10th page, 34th. Reference may be made to claim 1, patent document 12, on the line. These contents form part of this specification.
International Patent Publication No. WO-A-2007 / 077941 European Patent Publication No. EP-A-939071 International Patent Publication No. W02008 / 054781 International Patent Publication No. WO2008 / 040969

  The preferred embodiment uses a specific catalyst which is a hybrid supported catalyst containing both chromium and nickel. The molar ratio of Cr: Ni to metal element is generally between 0.5 and 5, preferably between 0.7 and 2, close to 1. The catalyst may contain 0.5-20% chromium by weight and 0.5-20% nickel, preferably between 2-10% of each metal.

  The metal in the catalyst is converted to a metal derivative during activation (or regeneration), such as an oxide, halide or oxyhalide.

As far as the supported catalyst is concerned, the catalyst support can be selected from materials well known to those skilled in the art that can be mixed with HF at higher temperatures and pressures. For example, fluorinated alumina, pre-fluorinated activated carbon, graphite or fluorinated graphite are suitable catalyst supports.
The support is preferably aluminum. Other supports such as alumina, activated alumina or aluminum derivatives can also be used. These derivatives include, for example, aluminum halides and aluminum halide oxides described in Patent Document 13, and are obtained by an activation method.
U.S. Pat. No. 4,902,838

With regard to the catalyst, it is possible to refer to Patent Document 14, in particular, page 4, line 30 to page 7, line 16. This content forms part of the present specification.
International Patent Publication No. WO 2009/118628

In another embodiment, the process of the present invention preferably uses an unsupported high surface area Cr-based catalyst. A preferred catalyst is a high surface area unsupported chromium oxide catalyst.
The catalyst can optionally contain one or more cocatalysts, such as Co, Zn, Mn, Mg, V, Mo, Te, Nb, Sb, Ta, P and Ni salts, at low levels. A preferred cocatalyst is nickel. Another preferred cocatalyst is magnesium.

  Preferred unsupported chromium catalysts optionally further comprise a low level of one or more cocatalysts selected from cobalt, nickel, zinc or manganese prepared by impregnation, such as impregnation, mixed powders, etc. be able to.

The amount of cocatalyst (if present) can vary from 1 to 10% by weight, preferably from 1 to 5% by weight. The cocatalyst can be added to the catalyst by methods well known to those skilled in the art, such as by evaporating the solvent after adsorption from an aqueous or organic solution. The preferred catalyst in this example is pure chromium oxide with nickel or zinc as cocatalyst. In a variant, the cocatalyst can be physically mixed with the catalyst by grinding to produce a homogeneous mixture. Another catalyst is a chromium / nickel hybrid catalyst supported on fluorinated alumina. The following document (which is incorporated herein by reference) discloses a method for preparing this alternative catalyst.
US Pat. No. 5,731,481

The catalyst is subjected to a drying step before activation. Preferably a dry gas, preferably nitrogen, is passed. The drying step can be carried out at pressures from atmospheric to 20 bar. The temperature of the catalyst in the drying stage is from about 1 to 50 hours, preferably 5 to 20 hours, with a contact time of about 1 to 100 seconds, preferably about 10 to 40 seconds, from room temperature to 400 ° C., preferably about The temperature can be 100 ° C to about 200 ° C.
After the drying stage, it is necessary to activate the catalyst in order to achieve the highest level of catalyst activity.

Catalyst Activation The inventors have found that (optional) activation of the catalyst using an oxidant-containing gas stream can greatly improve the efficiency of the fluorination process.
This activation process involves activating the catalyst in two stages or in a single stage using one or two activators. One activator is an oxidizing agent, such as oxygen or an oxygen / nitrogen mixture or air or chlorine. The other activator (if present) can be HF.

  In one embodiment of the present invention, the activation process is a two-stage activation process, first using an oxidant as the first activator and then using HF as the second activator. First, the new catalyst is treated with an oxidant. The temperature of this activation step can be from about 250 to about 500 ° C., preferably from about 300 to about 400 ° C., and the contact time can be from about 1 to about 200 seconds for about 10 to about 200 hours. The catalyst is then treated with HF. The temperature of the activation stage using HF as the activator is about 100 to about 450 ° C., preferably about 200 to about 300 ° C., for about 1 to about 50 hours, and the contact time is about 1 to about 100 seconds. Can do.

  In another embodiment of the present invention, the activation process is a two-stage activation process, first using HF as the first activator and then using the oxidizing agent as the second activator. First, the new catalyst is treated with HF. The temperature of this activation stage can be from about 100 to about 450 ° C., preferably from about 200 to about 300 ° C., for about 1 to about 50 hours, and the contact time can be from about 1 to about 100 seconds. The catalyst is then treated with an oxidant. The temperature of this activation step can be from about 250 to about 500 ° C., preferably from about 300 to about 400 ° C., and the contact time can be from about 1 to about 200 seconds for about 10 to about 200 hours.

  In yet another embodiment, the activation process is a two-step activation process that includes an activation performed by first performing a fluorination reaction followed by activation with an oxidant. The fluorination reaction can be performed for about 6 to about 100 hours (for example, 50 hours or less). The HF molar ratio during the fluorination reaction can be from about 2 to about 40. The temperature of the activation step using the oxidizing agent can be about 250 to about 500 ° C., preferably about 300 to about 400 ° C. for about 10 to about 100 hours, and the contact time can be about 1 to about 200 seconds. . Both steps can be repeated until the catalyst activity reaches its highest level.

  In yet another embodiment, the activation process is a one-step activation process using HF and an oxidizing agent. The ratio of oxidizer in the HF and oxidizer mixture can be from about 2 to about 98 mole percent. The temperature of the activation stage can be from about 200 to about 450 ° C. for about 10 to about 200 hours, and the contact time can be about 1 to about 200 seconds.

  In yet another embodiment, the activation process is a one-step activation process using only an oxidant (no HF). The temperature of this activation step can be from about 250 to about 500 ° C., preferably from about 300 to about 400 ° C., for about 10 to about 300 hours, and the contact time can be about 1 to about 200 seconds.

The activation process can be carried out at pressures from atmospheric to about 20 bar.
In the above activation step using HF, HF can be supplied to the system together with an inert gas, such as nitrogen. The proportion of HF can be from about 1 to about 100 mole percent of the mixture.
In the above activation step using an oxidant, the oxidant can be supplied to the system together with an inert gas such as nitrogen. The ratio of oxygen or chlorine can be from about 1 to about 100 mole percent of the mixture.

  Activation with the oxidant-containing gas stream is at least 1 hour, preferably at least 2 hours, more preferably at least 4 hours, more preferably at least 10 hours, even more preferably at least 15 hours, 250-500 ° C., preferably 300 It is preferable to perform at a temperature of ˜400 ° C., more preferably 350 to 380 ° C. For example, a temperature of about 370 ° C. is appropriate.

  When the activation process includes two stages (eg, one stage using a first activator and the other stage using a second activator), these stages are performed once, twice or more Can be repeated alternately.

Catalyst regeneration The inventor further finds that the efficiency of the fluorination reaction tends to decrease with time, but that by performing a regeneration step on the catalyst, it can be increased again to the initial efficiency and even higher. It was. In the regeneration stage, as in the initial activation stage, the catalyst is contacted with an oxidant-containing gas stream.

  In one embodiment of the invention, each regeneration stage is a one-stage regeneration stage and is performed using oxygen or air or an oxygen / nitrogen mixture. The regeneration stage temperature can be about 250 to about 500 ° C. for about 10 to about 200 hours, and the contact time can be about 1 to about 200 seconds. The regeneration step can be carried out at pressures from atmospheric pressure to about 20 bar.

  In another embodiment, each regeneration stage is a single stage regeneration stage and is performed using oxygen or air or an oxygen / nitrogen mixture and HF. The regeneration stage temperature can be about 250 to about 500 ° C. for about 10 to about 200 hours, and the contact time can be about 1 to about 200 seconds. The regeneration step can be carried out at pressures from atmospheric pressure to about 20 bar. The proportion of oxygen can be about 2 to about 98 mole percent with respect to the mixture of oxygen and HF, and can be about 20 to about 100 mole percent with respect to the mixture of oxygen and nitrogen.

  When the reaction stage and the regeneration stage are alternately repeated, the time of each reaction stage can be 50 to 2000 hours, preferably 200 to 1000 hours, and the time of each regeneration stage is 10 to 200 hours, preferably 15 to It can be 60 hours.

Examples of the present invention will be described below, but the present invention is not limited to the following examples.
The equipment used consisted of an INCONEL® alloy 600 tubular reactor surrounded by a tubular oven and having an inner diameter of 19 mm. The reactor further comprises a pressure and temperature control device. The reactants are premixed with a static stirrer and made into a gas phase and introduced into the top of the reactor.
At the outlet of the reactor, a sample of the reaction product was taken, washed with a pre-column, and analyzed online by gas phase chromatography equipped with a low polarity capillary column.

  Analysis by gas phase chromatography is performed using a column CP Sil 8CB (dimensions 50 m × 0.32 mm × 5 μm) and a packed column 1% SP1000 / carbopack B, 60/80 mesh 5 m long. The temperature of the oven is first temperature: 40 ° C. for 10 minutes, then 250 ° C. with a gradient of 10 ° C./minute, and the second temperature: 40 ° C. for 20 minutes, then 10 ° C./minute Was programmed to 180 ° C.

  When xi is the initial molar amount of the material and xf is the total final molar amount of the material, the conversion (%) is (xi−xf) / xi × 100. Product selectivity is calculated from the ratio of the recovered molar amount of this product to the sum of the molar amounts of product resulting from the reaction of the material.

Air is added to maintain catalytic activity.
The contact time is defined by the ratio of the catalyst bed volume to the total flow volume under the experimental conditions of temperature and pressure. The molar ratio of HF is defined by the ratio of the molar flow rate of HF to the molar flow rate of HFCO-1233xf. The molar ratio of oxygen is defined by the ratio of the molar flow rate of oxygen to the molar flow rate of HFCO-1233xf.

Example 1
Fluorination of HFCO-1233xf:
Fluorination of HFCO-1233xf was performed in the reactor using a 73 cm ³ Ni-Cr catalyst supported on activated A1F _{3 which} was first fluorinated and then treated with air .
The catalyst used was a Ni / Cr atomic ratio = 1 hybrid nickel / chromium catalyst supported on fluorinated alumina, impregnated with a solution of nickel and anhydrous chromium (CrO ₃ ), and after impregnation and drying, the solid was obtained in 320%. It was made by treatment in the presence of a mixture of hydrofluoric acid and nitrogen (the concentration of the acid in the nitrogen was 5-10% by volume) at a temperature between 0 ° C. and 390 ° C.
In the activation process, (1) catalytic fluorination is carried out by a fluorination reaction carried out at a temperature of 340 ° C. for 46 hours at a contact time of 6 to 12 seconds, a molar ratio of HF of 23, 4 mol% oxygen per mole of HFCO 1233xf (2) It was treated under air at 370 ° C. and 1.5 L / hour for 64 hours.
Anhydrous HF was continuously supplied to the reactor at a rate of 8.1 g / hour and HFCO-1233xf at a rate of 2.2 g / hour under atmospheric pressure. Accordingly, the contact time was 12.2 seconds, the molar ratio of HF was 24, and the reaction temperature was 350 ° C. The amount of oxygen is 4 mol% with respect to the amount of HFCO-1233xf. The conversion of HFCO-1233xf is 40.8%. All the results are shown in [Table 1].

Example 2
Fluorination of HFCO-1233xf:
The catalyst of Example 1 was reused after being regenerated. The same catalyst as in Example 1 was used, and the regeneration stage was carried out by treating in air at 1.5 l / hour and 370 ° C. for 16 hours. Next, anhydrous HF was continuously supplied to the reactor at a rate of 4.4 g / hour and HFCO-1233xf at a rate of 1.2 g / hour continuously under atmospheric pressure for 100 hours. Therefore, the contact time was 22.4 seconds, the molar ratio of HF was 24, and the reaction temperature was 350 ° C. The amount of oxygen is 9 mol% with respect to the amount of HFCO-1233xf. Although the conversion was 64.4%, catalyst deactivation was observed over time, and the conversion finally reached 33.4%. All the results are shown in [Table 1].

Example 3
Fluorination of HFCO-1233xf:
Fluorination of HFCO-1233xf was carried out in the reactor using 73 cm ³ Ni—Cr catalyst supported on A1F ₃ as described in Example 1 which was first fluorinated and then treated with air .
The activation process was cycled 5 times as follows: (1) Implementation of catalytic fluorination by fluorination reaction performed for 6 to 30 hours under the following conditions, followed by (2) 1.5 L / in by air at 370 ° C. Hour, treatment of catalyst for 16-64 hours.
For the purpose of the fluorination reaction, anhydrous HF was continuously supplied to the reactor at a rate of 3.4 g / hour and HFCO-1233xf at 1 g / hour under atmospheric pressure. Accordingly, the contact time was 29 seconds, the HF molar ratio was 22, and the reaction temperature was 350 ° C. The amount of oxygen is 7-8 mol% with respect to the amount of HFCO-1233xf. The conversion is 69.7% and decreases to 54.7% over time. The regeneration phase was then carried out for 16 hours under 1.5 L / hour of 370 ° C. air. After this stage, a higher conversion (72.4%) was recovered than the conversion observed initially. All the results are shown in [Table 1].

Example 4 (Comparative Example)
Fluorination of HFCO-1233xf:
Activation with HF alone Fluorination of HFCO-1233xf was carried out in the reactor using a 73 cm ³ Ni—Cr catalyst supported on A1F ₃ as described in Example 1.
After activating the catalyst with HF at 350 ° C. at atmospheric pressure without treatment under air, the reactor was charged with anhydrous HF at a rate of 7.6 g / hr and HFCO-1233xf at a rate of 2.2 g / hr under atmospheric pressure. Continuously fed. Accordingly, the contact time was 12.7 seconds, the molar ratio of HF was 23, and the reaction temperature was 350 ° C. The amount of oxygen is 4 mol% with respect to the amount of HFCO-1233xf. The conversion of HFCO-1233xf was 9.1%.

Example 5 (Comparative Example)
Fluorination of HFCO-1233xf without specific activation Fluorination of HFO-1233xf was carried out in the reactor using 73 cm ³ Ni—Cr catalyst supported on A1F ₃ as described in Example 1.
After adding the catalyst to the reactor, the catalyst was dried with nitrogen at 220 ° C. for 16 hours. The reactor temperature was then brought to 350 ° C., and anhydrous HF was continuously fed to the reactor at 350 ° C. at atmospheric pressure at a rate of 4.5 g / hr, HFCO-1233xf and air. did. The contact time was 22 seconds and the HF MR was 24. The amount of oxygen is 9 mol% with respect to the amount of HFCO-1233xf. After 24 hours reaction, the conversion of HFCO-1233xf reached 14.8%.
All results are shown in [Table 2].

Example 6
Fluorination of HFCO-1233xf:
Activation with air alone Fluorination of HFCO-1233xf was carried out in the reactor using a 73 cm ³ Ni—Cr catalyst supported on A1F ₃ as described in Example 1.
First, the catalyst was dried with nitrogen at 220 ° C. for 16 hours. The nitrogen supply was then stopped and air was introduced into the reactor for 2 hours. The oven temperature was then brought to 370 ° C. and maintained at this temperature for 64 hours. After this activation of the catalyst, the oven temperature and air flow rate were adjusted for the following experiments. Anhydrous HF was continuously fed to the reactor at a rate of 5.0 g / hr and HFCO-1233xf was 1.1 g / hr continuously under atmospheric pressure. The contact time was 20 seconds and the HF MR was 30. The reaction temperature was 350 ° C. The amount of oxygen is 9 mol% with respect to the amount of HFCO-1233xf. After 22 hours of reaction, the conversion of HFCO-1233xf reached 18.5%.
All results are shown in [Table 2].

Example 7
Fluorination of HFCO-1233xf:
Activation with HF followed by air Fluorination of HFCO-1233xf was carried out in the reactor using a 73 cm ³ Ni—Cr catalyst supported on A1F ₃ as described in Example 1.
First, the catalyst was dried under atmospheric pressure with nitrogen at 220 ° C. for 16 hours. HF was then introduced and maintained for 2 hours. The oven temperature was 350 ° C. and maintained with HF for 3 hours. The HF was then replaced with air at 1.5 l / hour and the oven temperature was brought to 370 ° C. and maintained for 16 hours. The oven temperature and air flow rate were then adjusted for the following experiment and HF and HFCO-1233xf were introduced into the reactor. Anhydrous HF was continuously supplied to the reactor at a rate of 4.1 g / hour and HFCO-1233xf was supplied at a rate of 1.0 g / hour under atmospheric pressure. The contact time was 24 seconds and the HF MR was 26. The reaction temperature was 350 ° C. The amount of oxygen is 8 mol% with respect to the amount of HFCO-1233xf. After 10 hours of reaction, the conversion of HFCO-1233xf reached 58.6%.
All results are shown in [Table 2].

Claims (20)

  A fluorination method comprising alternately a reaction stage and a regeneration stage, wherein the reaction stage comprises reacting a chlorinated product with hydrogen fluoride in the gas phase in the presence of a fluorination catalyst to produce a fluorinated product. Contacting the fluorination catalyst with an oxidant-containing gas stream.   The fluorination method of claim 1, further comprising a preactivation step comprising contacting the fluorination catalyst with an oxidant-containing gas stream.   The process according to claim 1 or 2, wherein the oxidant-containing gas stream of the activation stage and / or the regeneration stage is an oxygen-containing gas stream.   The activation and / or regeneration step comprises contacting the fluorination catalyst with an oxidant-containing gas stream for at least 2 hours, preferably at least 4 hours, more preferably at least 10 hours, and even more preferably at least 15 hours. The method as described in any one of 1-3.   The oxidant-containing gas stream of the activation stage and / or regeneration stage contains hydrogen fluoride in addition to the oxidizer, and the ratio of oxidizer in the oxidant-containing gas stream of the activation stage and / or regeneration stage is oxidized Preferably it is 2-98 mol% with respect to the total amount of an agent and hydrogen fluoride, More preferably, it is 5-50 mol%, The method as described in any one of Claims 1-4.   6. Process according to any one of claims 1 to 5, wherein the oxidant-containing gas stream of the activation stage and / or regeneration stage is free of hydrogen fluoride, preferably air. The process according to any one of the preceding claims, wherein the activation and / or regeneration stage comprises contacting the fluorination catalyst with a hydrogen fluoride gas stream in (1) or (2) below:
(1) before contacting the fluorination catalyst with the oxidant-containing gas stream, or (2) after contacting the fluorination catalyst with the oxidant-containing gas stream.   8. The activation step according to any one of the preceding claims, wherein the activation step comprises a preliminary step of gas phase reaction of the chlorinated product with hydrogen fluoride in the presence of a fluorination catalyst prior to contacting the chlorinated product with the oxidant containing gas stream. The method according to item.   9. The oxidant-containing gas stream is contacted with the fluorination catalyst at a temperature of 250-500 ° C., preferably 300-400 ° C., more preferably 350-380 ° C. in the activation stage and / or regeneration stage. The method according to claim 1.   The process according to any one of claims 1 to 9, wherein the fluorinated product is a fluoroolefin, preferably fluoropropene, more preferably 2,3,3,3-tetrafluoro-1-propene.   Chlorides are selected from hydrochlorocarbons, hydrochlorofluorocarbons and hydrochlorofluoroolefins, preferably 2-chloro-3,3,3-trifluoro-1-propene, 1,1,1,2,3-penta Chloropropane, 1,1,2,2,3-pentachloropropane, 2,3-dichloro-1,1,1-trifluoropropane, 2,3,3,3-tetrachloro-1-propene and 1,1, 11. A process according to any one of the preceding claims, selected from 2,3-tetrachloro-1-propene, more preferably 2-chloro-3,3,3-trifluoro-1-propene.   The fluorination catalyst is a supported catalyst, preferably supported on a support selected from fluorinated alumina, fluorinated chromia, fluorinated activated carbon or graphite carbon. The method according to item.   The method according to any one of claims 1 to 11, wherein the fluorination catalyst is an unsupported catalyst.   The fluorination catalyst further comprises a cocatalyst selected from Co, Zn, Mn, Mg, V, Mo, Te, Nb, Sb, Ta, P, Ni or mixtures thereof, preferably Ni, and 15. A process according to any one of the preceding claims, wherein the cocatalyst is preferably present in an amount of about 1-10% by weight of the fluorination catalyst.   The process according to any one of the preceding claims, wherein the fluorination catalyst is a hybrid chromium / nickel catalyst in which the atomic ratio of nickel to chromium is preferably 0.5-2, more preferably about 1.   The molar ratio of hydrogen fluoride: 2-chloro-3,3,3-trifluoro-1-propene is 3: 1 to 150: 1, preferably 4: 1 to 70: 1, more preferably 5: 1 to 50. 16. The method according to any one of claims 1 to 15, wherein the ratio is 1: 1, more preferably 10: 1 to 30: 1.   Process according to any one of the preceding claims, wherein the reaction stage is carried out at a pressure of 1 to 20 bar, preferably 5 to 15 bar, more preferably 7 to 10 bar.   The process according to any one of claims 1 to 17, wherein the reaction stage is carried out at a temperature of 200 to 450 ° C, preferably 300 to 430 ° C, more preferably 320 to 420 ° C, more preferably 340 to 380 ° C.   The contact time between hydrogen fluoride and chlorinated product in the reaction stage is 6 to 100 seconds, preferably 10 to 80 seconds, more preferably 15 to 50 seconds. Method.   The reaction stage is carried out in the presence of 0.05 to 15 mol%, more preferably 0.5 to 10 mol%, more preferably 5 to 10 mol% of an oxidant, for example oxygen, based on the total amount of chlorinated products and oxygen. 20. A method according to any one of the preceding claims, wherein the method is carried out.